Maleinized ester derivatives

ABSTRACT

This disclosed invention relates to a maleinated ester derivative derived from an unsaturated linear aliphatic carboxylic acid methyl ester, maleic anhydride, and a monohydric alcohol. Lubricants and functional fluids containing the maleinated esters are disclosed.

A claim of priority under 35 U.S.C. §119(e) is hereby made to U.S.Provisional Application 61/776,952 filed Mar. 12, 2013. This provisionalapplication is incorporated herein by reference.

TECHNICAL FIELD

This invention relates to maleinized ester derivatives and, moreparticularly, to maleinized ester derivatives derived from unsaturatedlinear aliphatic carboxylic acid methyl esters, maleic anhydride, andmonohydric alcohols. The invention relates to lubricants and functionalfluids containing the maleinized ester derivatives.

BACKGROUND

Synthetic lubricants may be used in passenger car motor oils, heavy-dutydiesel engine oils, marine and railroad engine lubricants, automatictransmission fluids, hydraulic fluids, gear oils, and industriallubricants, such as metalworking fluids and lubricating greases.

SUMMARY

The purpose of these synthetic lubricants is to provide improvedfriction and wear control, rapid dissipation of heat, and thedissolution of and/or facilitating the removal of service-relatedcontaminants. Achieving a proper balance between various performancecharacteristics is an important consideration in selecting a syntheticlubricant for a particular application. For example, polyolefin basedlubricants typically exhibit good low-temperature properties, highviscosity index, and excellent thermal stability, but poor solvency. Asa result, these lubricants tend to be inadequate without the presence ofadditional polar base stock-containing components. Conversely, polarbase stock-containing lubricants, such as those based on syntheticesters and vegetable oils, typically exhibit good solvency and highsurface affinity. However, these lubricants tend to be inadequate withrespect to resistance to wear. The problem, therefore, is to provide asynthetic lubricant that exhibits both good solvency and good resistanceto wear reduction characteristics. This invention provides a solution tothis problem.

This invention relates to a composition comprising a maleinized esterderivative made by the reaction of: (i) an unsaturated linear aliphaticcarboxylic acid methyl ester comprising a linear hydrocarbon chain ofabout 8 to about 18 carbon atoms, or about 10 to about 14 carbon atoms,or about 12 carbon atoms; maleic anhydride; and a monohydric alcohol of3 to about 12 carbon atoms, or 3 to about 10 carbon atoms, or 3 to about8 carbon atoms, or about 5 to about 10 carbon atoms, or about 5 carbonatoms; wherein the maleinized ester derivative comprises at least twoproximal ester groups and another ester group, the proximal ester groupsand the another ester group containing straight chain alkyl groups of 3to about 12 carbon atoms, or 3 to about 8 carbon atoms, or about 5carbon atoms; the proximal ester groups being separated from the anotherester group by at least about 8 carbon atoms, or at least about 9 carbonatoms, or at least about 10 carbon atoms.

When counting the number of carbon atoms separating two ester groups,the carbonyl atoms of each ester group are included. For example, twoproximal ester groups formed on a maleic anhydride group are separatedby two carbon atoms, but when including the carbonyl atoms of the estergroup, the proximal ester groups are separated by four carbon atoms.Similarly, when counting the number of carbon atoms between a proximalester group and the another ester group, the carbonyl atoms of eachester group are included.

The monohydric alcohol may be linear or branched. In an advantageousembodiment of the invention, the monohydric alcohol comprises one ormore linear alcohols.

In any of the above-indicated embodiments, the unsaturated linearaliphatic carboxylic acid methyl ester is reacted with the maleicanhydride to form a maleinized unsaturated carboxylic acid methyl ester,and the maleinized unsaturated carboxylic acid methyl ester is reactedwith the monohydric alcohol to form the maleinized ester derivative.

In any of the above-indicated embodiments, prior to the reaction withthe monohydric alcohol, the maleinized carboxylic acid methyl estercomprises a methyl ester group and a maleic anhydride group, thereaction with the monohydric alcohol comprising an esterificationreaction with the maleic anhydride group and a transesterificationreaction with the methyl ester group.

In any of the above-indicated embodiments, prior to the reaction withthe monohydric alcohol, the maleinized carboxylic acid methyl estercomprises a methyl ester group and two maleic anhydride groups, thereaction with the monohydric alcohol comprising an esterificationreaction with the maleic anhydride groups and a transesterificationreaction with the methyl ester group.

In any of the above-indicated embodiments, the maleinized esterderivative comprises a mono-triester.

In any of the above-indicated embodiments, the maleinized esterderivative comprises a mixture of a mono-triester and a di-triester.

In any of the above-indicated embodiments, the maleinized ester isbiodegradable.

In any of the above-indicated embodiments, the maleinized esterderivative is biodegradable.

In any of the above-indicated embodiments, the maleinized esterderivative contains one or more carbon-carbon double bonds, thecarbon-carbon double bonds being hydrogenated to form saturated carbonbonds.

In any of the above-indicated embodiments, the unsaturated linearaliphatic carboxylic acid methyl ester comprises methyl 8-nonenoate,methyl 9-decenoate, methyl 10-undecenoate, methyl 9-dodecenoate, methyl9-octadecenoate, or a mixture of two or more thereof.

In any of the above-indicated embodiments, the monohydric alcoholcomprises 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol,1-octanol, 1-decanol, 1-undecanol, 1-dodecanol, 2-methyl butanol,3-methyl butanol, a C₁₀ branched alcohol, or a mixture of two or morethereof.

In any of the above-indicated embodiments, the unsaturated linearaliphatic carboxylic acid methyl ester comprises methyl 9-dodecenoateand the monohydric alcohol comprises 1-pentanol.

In any of the above-indicated embodiments, the unsaturated linearaliphatic carboxylic acid methyl ester is derived from a naturalproduct. The natural product may comprise vegetable oil, algae oil,fungus oil, animal oil, animal fat, sucrose, lactose, glucose, fructose,canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, oliveoil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil,sunflower seed oil, tall oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard oil, camellina oil, pennycress oil, castor oil,coriander oil, almond oil, wheat germ oil, bone oil, lard, tallow,poultry fat, algae oil, yellow grease, fish oil, sugar cane, sugar beet,corn syrup, or a mixture of two or more thereof.

These compositions may be useful as additives as well as base stocks forlubricant compositions and/or functional fluid compositions. Becausethese compositions may be derived from natural products, they may beclassified as renewable materials. This technology may be referred to as“green” technology.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow sheet illustrating a process within the scope of theinvention for reacting an unsaturated linear aliphatic carboxylic acidmethyl ester with maleic anhydride to form a maleinized unsaturatedcarboxylic acid methyl ester. The maleinized unsaturated carboxylic acidmethyl ester may be referred to as a maleinized ester intermediate.

FIG. 2 is a flow sheet illustrating a process within the scope of theinvention for esterifying a maleinized unsaturated carboxylic acidmethyl ester (or maleinized ester intermediate).

FIG. 3 is a chart showing conversions for the maleinization of methyl9-dodecenoate at reaction temperatures of 195° C., 205° C., 215° C. and230° C. over a reaction period of 12 hours.

FIG. 4 is a chart showing acid value plots for reactions of maleinizedmethyl 9-dodecenoate with 1-pentanol.

FIG. 5 is a schematic illustration of the test apparatus used in Example9.

DETAILED DESCRIPTION

All ranges and ratio limits disclosed in the specification and claimsmay be combined in any manner. It is to be understood that unlessspecifically stated otherwise, references to “a,” “an,” and/or “the” mayinclude one or more than one, and that reference to an item in thesingular may also include the item in the plural.

The phrase “and/or” should be understood to mean “either or both” of theelements so conjoined, i.e., elements that are conjunctively present insome cases and disjunctively present in other cases. Other elements mayoptionally be present other than the elements specifically identified bythe “and/or” clause, whether related or unrelated to those elementsspecifically identified unless clearly indicated to the contrary. Thus,as a non-limiting example, a reference to “A and/or B,” when used inconjunction with open-ended language such as “comprising” can refer, inone embodiment, to A without B (optionally including elements other thanB); in another embodiment, to B without A (optionally including elementsother than A); in yet another embodiment, to both A and B (optionallyincluding other elements); etc.

The word “or” should be understood to have the same meaning as “and/or”as defined above. For example, when separating items in a list, “or” or“and/or” shall be interpreted as being inclusive, i.e., the inclusion ofat least one, but also including more than one, of a number or list ofelements, and, optionally, additional unlisted items. Only terms clearlyindicated to the contrary, such as “only one of,” or “exactly one of,”or may refer to the inclusion of exactly one element of a number or listof elements. In general, the term “or” as used herein shall only beinterpreted as indicating exclusive alternatives (i.e. “one or the otherbut not both”) when preceded by terms of exclusivity, such as “either,”“one of,” “only one of,” or “exactly one of.”

The phrase “at least one,” in reference to a list of one or moreelements, should be understood to mean at least one element selectedfrom any one or more of the elements in the list of elements, but notnecessarily including at least one of each and every elementspecifically listed within the list of elements and not excluding anycombinations of elements in the list of elements. This definition alsoallows that elements may optionally be present other than the elementsspecifically identified within the list of elements to which the phrase“at least one” refers, whether related or unrelated to those elementsspecifically identified. Thus, as a non-limiting example, “at least oneof A and B” (or, equivalently, “at least one of A or B,” or,equivalently “at least one of A and/or B”) can refer, in one embodiment,to at least one, optionally including more than one, A, with no Bpresent (and optionally including elements other than B); in anotherembodiment, to at least one, optionally including more than one, B, withno A present (and optionally including elements other than A); in yetanother embodiment, to at least one, optionally including more than one,A, and at least one, optionally including more than one, B (andoptionally including other elements); etc.

The transitional words or phrases, such as “comprising,” “including,”“carrying,” “having,” “containing,” “involving,” “holding,” and thelike, are to be understood to be open-ended, i.e., to mean including butnot limited to.

The term “ester group” refers to a chemical group wherein a carbonyl isadjacent to an ether linkage. The ester group may be represented by theformula —COOR, wherein R is an alkyl group.

The term “proximal ester groups” refers to ester groups attached to thesame compound and positioned within no more than about four carbon atomsfrom each other. The ester groups formed by the esterification of amaleic anhydride group may be referred to as proximal ester groups.

The term “another ester group” refers to an ester group attached to acompound that also contains two or more proximal ester groups, theanother ester group not being one of the proximal ester groups.

The term “maleinized ester” refers to a product made by the reaction ofan unsaturated carboxylic acid methyl ester with maleic anhydride. Themaleinized ester may be referred to as a maleinized ester intermediate.

The term “maleinized ester derivative” refers to a product made by thereaction of a maleinized ester with a monohydric alcohol.

The term “unsaturated linear aliphatic carboxylic acid methyl ester”refers to a compound represented by the formula R—COOCH₃, wherein R isan unsaturated linear aliphatic hydrocarbon group (e.g., an alkenylgroup). Examples of the unsaturated linear aliphatic carboxylic acidmethyl esters that may be used include methyl 8-nonenoate, methyl9-decenoate, methyl 10-undecenoate, methyl 9-dodecenoate, methyl9-octadecenoate, or a mixture of two or more thereof.

The term “maleic anhydride” refers to a compound represented by theformula C₂H₂(CO)₂O. Maleic anhydride is the acid anhydride of maleicacid.

The term “monohydric alcohol” refers to a compound represented by theformula ROH, wherein R is a aliphatic hydrocarbon (e.g., alkyl) group. Rmay be branched or linear. In an advantageous embodiment, R is linear.Examples of the monohydric alcohols that may be used include 1-propanol,1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol,1-undecanol, 1-dodecanol, 2-methyl butanol, 3-methyl butanol, a C₁₀branched alcohol, or a mixture of two or more thereof.

The term “natural product” is used herein to refer to products ofnature, including natural oil, carbohydrates, and the like.

The term “natural oil” refers to oils or fats derived from plants oranimals. The term “natural oil” includes natural oil derivatives, unlessotherwise indicated, and such natural oil derivatives may include one ormore natural oil derived unsaturated carboxylic acids or derivativesthereof. The natural oils may include vegetable oils, algae oils, fungusoils, animal oils or fats, tall oils, derivatives of these oils,combinations of two or more of these oils, and the like. The naturaloils may include, for example, canola oil, rapeseed oil, coconut oil,corn oil, cottonseed oil, olive oil, palm oil, peanut oil, saffloweroil, sesame oil, soybean oil, sunflower seed oil, linseed oil, palmkernel oil, tung oil, jatropha oil, mustard oil, camellina oil,pennycress oil, castor oil, coriander oil, almond oil, wheat germ oil,bone oil, lard, tallow, poultry fat, yellow grease, fish oil, mixturesof two or more thereof, and the like. The natural oil (e.g., soybeanoil) may be refined, bleached and/or deodorized.

The natural product may comprise a refined, bleached and/or deodorizednatural oil, for example, a refined, bleached, and/or deodorized soybeanoil (i.e., RBD soybean oil). Soybean oil may comprises about 95% byweight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. The fatty acids in the soybean oil may include saturated fattyacids, including palmitic acid (hexadecanoic acid) and stearic acid(octadecanoic acid), and unsaturated fatty acids, including oleic acid(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

The term “carbohydrate” is used herein to refer to a class of compoundswith the empirical formula C_(m) (H₂O)_(n) that comprise carbon,hydrogen and oxygen atoms, with a hydrogen:oxygen ratio of 2:1. Anexample is deoxyribose which has the empirical formula C₅H₁₀O₄. Thecarbohydrates include the saccharides. The saccharides may include:monosaccharides, disaccharides, oligosaccharides, and polysaccharides.The monosaccharides and disaccharides may be referred to as sugars. Thesugars, which may be in the form of crystalline carbohydrates, mayinclude sucrose, lactose, glucose, fructose, fruit sugar, and the like.These may be obtained from sugar cane, sugar beet, corn syrup, and thelike.

The term “biodegradable” refers to a material that degrades to form CO₂and water.

The term “metathesis reaction” refers to a catalytic reaction whichinvolves the interchange of alkylidene units among compounds containingone or more carbon-carbon double bonds (e.g., olefinic compounds) viathe formation and cleavage of the carbon-carbon double bonds. Metathesismay occur between two like molecules (often referred to asself-metathesis) and/or between two different molecules (often referredto as cross-metathesis).

The term “metathesis catalyst” refers to any catalyst or catalyst systemthat catalyzes a metathesis reaction.

Maleinized Ester

The maleinized ester may be formed by the reaction of an unsaturatedlinear aliphatic carboxylic acid methyl ester with maleic anhydride. Themaleinized ester may be referred to as a maleinized ester intermediate.The maleinized ester derivative may be formed by reaction of themaleinized ester with a monohydric alcohol.

The unsaturated linear aliphatic carboxylic acid methyl ester maycomprise an unsaturated linear aliphatic hydrocarbon chain (e.g., analkenyl chain) of from about 8 to about 18 carbon atoms, or from about10 to about 14 carbon atoms, or from about 10 to about 12 carbons, orabout 12 carbon atoms, with one or more carbon-carbon double bonds inthe hydrocarbon chain. The unsaturated linear aliphatic carboxylic acidmethyl ester may be monounsaturated or polyunsaturated with, forexample, from 1 to about 4, or 1 to about 3, or 1 or 2, or 1carbon-carbon double bonds. When the hydrocarbon chain contains morethan one carbon-carbon double bond, it may be partially hydrogenated toform a mono-unsaturated compound prior to being maleinized.

The unsaturated linear aliphatic carboxylic acid methyl ester maycomprise methyl 8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate,methyl 9-dodecenoate, methyl 9-octadecenoate, or a mixture of two ormore thereof.

The unsaturated linear aliphatic carboxylic acid methyl ester may bederived from one or more natural products, including natural oil,carbohydrates, and the like. The unsaturated linear aliphatic carboxylicacid methyl ester may be derived from an estolide. The unsaturatedlinear aliphatic carboxylic acid methyl ester may be derived from apolyol ester, for example, a monoglyceride, diglyceride, triglyceride,or a mixture of two or more thereof.

The natural product may comprise one or more oils or fats derived fromplants and/or animals. The natural oils may include vegetable oils,algae oils, fungus oils, animal oils or fats, tall oils, derivatives ofthese oils, combinations of two or more of these oils, and the like. Thenatural product may comprise one or more carbohydrates. The naturalproducts may include sucrose, lactose, glucose, fructose, canola oil,rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palmoil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower seedoil, linseed oil, palm kernel oil, tung oil, jatropha oil, mustard oil,camellina oil, pennycress oil, castor oil, tall oil, coriander oil,almond oil, wheat germ oil, bone oil, lard, tallow, poultry fat, yellowgrease, fish oil, bone oil, mixtures of two or more thereof, and thelike. The natural product may be a natural oil (e.g., soybean oil) whichis refined, bleached and/or deodorized.

The natural product may comprise soybean oil. Soybean oil may compriseunsaturated glycerides, for example, in many embodiments about 95%weight or greater (e.g., 99% weight or greater) triglycerides. Majorfatty acids making up soybean oil may include saturated fatty acids,palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid),and unsaturated fatty acids, oleic acid (9-octadecenoic acid), linoleicacid (9,12-octadecadienoic acid), and linolenic acid(9,12,15-octadecatrienoic acid). Soybean oil may be a highly unsaturatedvegetable oil with many of the triglyceride molecules having at leasttwo unsaturated fatty acids. The soybean oil may be refined, bleachedand/or deodorized.

The unsaturated linear aliphatic carboxylic acid methyl ester may bederived from a natural product using a metathesis reaction process.Metathesis is a catalytic reaction that involves an interchange ofalkylidene units among compounds containing one or more carbon-carbondouble bonds (i.e., olefinic compounds). The reaction mechanism involvescleavage and formation of carbon-carbon double bonds. Metathesis canoccur between two of the same molecules (often referred to asself-metathesis) and/or it can occur between two different molecules(often referred to as cross-metathesis). The self-metathesis process maycomprise reacting a natural product such as a natural oil or natural oilderived unsaturated carboxylic acid and/or ester in the presence of ametathesis catalyst to form a metathesized natural product.

The cross-metathesis process may comprise reacting a natural productsuch as a natural or natural oil derivative with another olefiniccompound in the presence of a metathesis catalyst to form a productmixture containing the desired unsaturated carboxylic acid methyl ester.The another olefinic compound may be a natural product, natural oil,natural oil derivative or a short chain olefin. The short chain olefinmay comprise an alpha olefin, an internal olefin, or a mixture thereof.The internal olefin may be symmetric or asymmetric. The olefin maycomprise one or more of ethene, propene, 2-butene, 3-hexene, 4-octene,2-pentene, 2-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene,3-nonene, 4-nonene, ethylene, 1-propene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene,1-eicosene, or a mixture of two or more thereof.

The catalyst used in the metathesis reaction may be any catalyst orcatalyst system which catalyzes the metathesis reaction. The metathesiscatalyst may be used, alone or in combination with one or moreadditional catalysts. Exemplary metathesis catalysts may include metalcarbene catalysts based upon transition metals, for example, ruthenium,molybdenum, osmium, chromium, rhenium, and/or tungsten. Examples ofmetathesis catalysts and process conditions are described in US2011/0160472, incorporated by reference herein in its entirety, exceptthat in the event of any inconsistent disclosure or definition from thepresent specification, the disclosure or definition herein shall bedeemed to prevail. A number of the metathesis catalysts described in US2011/0160472 are presently available from Materia, Inc. (Pasadena,Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

The product produced by the metathesis reaction may comprise one or moreunsaturated carboxylic acids and/or esters. These may include glyceridesand free fatty acids and/or esters. The acids and/or esters may be usedas a source for the unsaturated carboxylic acid methyl esters of thepresent invention. In an embodiment, further processing may target, forexample, C₈-C₁₈ fatty acid methyl esters. These may include methyl8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, methyl9-dodecenoate, methyl 9-octadecenoate, or a mixture of two or morethereof.

The natural product and/or natural product derived unsaturatedcarboxylic acid and/or ester may be partially hydrogenated prior toundergoing the metathesis reaction. Multiple unsaturated bonds within apolyunsaturated reactant provide multiple reaction sites. Multiplereaction sites may increase the chemical identity of the reactionproducts, which in turn may increase the complexity of the productcomposition. Multiple reaction sites within the reactants may alsoincrease catalyst demand for the reaction. These factors may increasethe overall complexity and inefficiency of the reaction process. Moreefficient reaction processes that can reduce catalyst demand and reducecomplexity of the reaction product compositions may be provided bypartially hydrogenating polyunsaturated reactants in the startingmaterial prior to conducting the metathesis reaction process.

The unsaturated linear aliphatic carboxylic acid methyl esters may bepartially hydrogenated prior to being reacted with the maleic anhydrideto form the maleinized esters.

The hydrogenation reactions, as well as the metathesis reactions, andcatalysts for such reactions, that may be used are described in moredetail in U.S. patent publication 2012-0264664A1.

The reaction between the unsaturated linear aliphatic carboxylic acidmethyl ester and the maleic anhydride to form the maleinized ester maybe a thermal reaction conducted without a catalyst, or it may be acatalytic reaction. The catalyst may comprise a dialkylperoxide, or aLewis acid such as AlCl₃. The reaction temperature may be in the rangefrom about 100° C. to about 300° C., or from about 150° C. to about 250°C., or from about 195° C. to about 240° C., or about 220° C. to about240° C., or about 230° C. Lab studies for the maleinization of methyl9-dodecenoate at reaction temperatures of 195° C., 205° C., 215° C. and230° C. are shown in FIG. 3. A useful temperature for the maleinizationof methyl 9-dodecenoate is 230° C. with a reaction time of 8 hours.

The molar ratio of equivalents of the unsaturated linear aliphaticcarboxylic acid methyl ester to equivalents of the maleic anhydride maybe from about 0.5:1 to about 4:1, or from about 1:1 to about 2:1. Theweight of an equivalent of an unsaturated linear aliphatic carboxylicacid methyl ester as well as maleic anhydride is dependent on the numberof carbon-carbon double bonds in the molecular structure of thecompounds. For example, one mole of an unsaturated linear aliphaticcarboxylic acid methyl ester having one carbon-carbon double bond in itsmolecular structure would have an equivalent weight equal to itsmolecular weight. Maleic anhydride, with one carbon-carbon double bond,has a equivalent weight equal to its molecular weight.

The amount of catalyst added to the reaction, when used, may be up toabout 15 percent by weight of the unsaturated linear aliphaticcarboxylic acid methyl ester, or from about 5 to about 15 percent byweight, or from about 5 to about 10 percent by weight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere. The time of reaction may range from about 1 toabout 24 hours, or from about 6 to about 18 hours, or from about 10 toabout 16 hours, or about 8 hours.

Following the reaction, the product mixture may be subjected toisolation of the crude material. The crude material may be subjected toa vacuum to separate undesired volatile materials from the product whichmay be referred to as a maleinized ester.

The maleinized ester may comprise the product made by the reaction ofmaleic anhydride with an unsaturated linear aliphatic carboxylic acidmethyl ester comprising methyl 8-nonenoate, methyl 9-decenoate, methyl10-undecenoate, methyl 9-dodecenoate, methyl 9-octadecenoate, or amixture of two or more thereof.

The maleinization of an unsaturated linear aliphatic carboxylic acidmethyl ester to form a maleinized ester within the scope of theinvention is shown below. The specific reaction that is shown is for themaleinization of methyl 9-dodecenoate. Some di-maleinization of themono-maleinized materials may occur by the addition of a second maleicanhydride molecule to the mono-maleinized material. This reaction mayproduce about 3-5 wt % of the di-maleinized material in the reactionmixture. Isomers for the ene reaction that are believed to form areshown, however the 9,10 di-substitution may not occur for sterichindrance reasons and the isomer shown with a terminal double bond maybe energetically unlikely.

Maleinized Ester Derivative

The maleinized ester derivative of the invention may be made by reactingthe above-indicated maleinized ester with a monohydric alcohol. Themonohydric alcohol may be linear or branched. In an advantageousembodiment, the alcohol is linear. The monohydric alcohol may contain 3to about 12 carbon atoms, or 3 to about 10 carbon atoms, or 3 to about 8carbon atoms, or about 5 to about 10 carbon atoms, or about 5 carbonatoms. The monohydric alcohol may comprise 1-propanol, 1-butanol,1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-undecanol,1-dodecanol, 2-methyl butanol, 3-methyl butanol, a C₁₀ branched alcohol,or a mixture of two or more thereof.

The ratio of C═O groups in the maleinized ester to —OH groups in themonohydric alcohol may be from about 1 to about 6, or from about 1 toabout 3, or from about 1 to about 2, or about 1.

The reaction between the maleinized ester and the monohydric alcohol maybe carried out in the presence of a catalyst. The catalyst may be aLewis acid or a Broonsted acid. These may include one or more sulfonicacids. The catalyst may comprise methane sulfonic acid. The reaction maybe enhanced by heating the reaction mixture to a temperature in therange from about 100° C. to about 250° C., or from about 100° C. toabout 200° C., or from about 150° C. to about 200° C., or from about160° C. to about 170° C.

The amount of catalyst added to the reaction may be from about 0.5percent by weight to about 10 percent by weight of the maleinized ester,or from about 2 to about 4 percent by weight, or 3 percent by weight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere. The time of reaction may range from about 4 toabout 12 hours, or from about 6 to about 12 hours, or from about 8 toabout 10 hours.

The reaction may be conducted at a pressure above atmospheric pressure,for example, in a stainless steel reactor with a back-pressureregulator. The internal pressure of the reaction may range from a gaugepressure of about 0 to about 60 psig (about 0 to about 414 kilopascals),or from about 30 to about 50 psig (about 207 to about 345 kilopascals),or about 45 psig (about 310 kilopascals).

The maleinized ester derivative formed by the reaction of the maleinizedester with the monohydric alcohol may comprise a triester. The triestermay comprise a mono-triester, or a mixture of a mono-triester and adi-triester. The maleinized ester derivative can have up to three estergroups on the mono-maleinized molecules and up to five ester groups onthe di-maleinized molecules.

The mechanism for the reaction of the maleinized ester with themonohydric alcohol may involve three reactions. The first reaction takesplace with the anhydride ring opening and forming a half ester whichincludes an ester group and a free carboxylic acid group. The freecarboxylic acid group then reacts with the alcohol and forms a diester.In addition, transesterification of the methyl ester group with themonohydric alcohol results in the formation of a triester.Representative structures for the reaction of maleinized methyl9-dodecenoate and 1-pentanol are shown below.

Pentanol half ester of the maleinized methyl 9-dodecenoate

Di-pentanol ester of the maleinized methyl 9-dodecenoate

Tri-pentanol ester of the maleinized methyl 9-dodecenoate

The initial ring opening reaction with the monohydric alcohol mayproduce no byproducts. The esterification of the carboxylic acid withthe monohydric alcohol is a reversible reaction and produces water as abyproduct. The water is removed in order to shift the equilibrium to theester and reduce the overall acidity of the product. Thetransesterification of the methyl ester with the monohydric alcoholproduces methanol as a byproduct. This reaction is also reversible. Themethanol is removed in order to drive the reaction towards themonohydric alcohol ester. The esterification and transesterificationreactions may be driven to completion by using an excess of themonohydric alcohol and by removing the byproducts of reaction, water andmethanol.

The progress of the reaction may be monitored by measuring the acidvalue (AV) of the reaction mixture. For example, AV plots for thereaction of maleinized methyl 9-dodecenoate and 1-pentanol are shown inFIG. 4.

The maleinized ester derivatives formed by the reaction of maleinizedesters with monohydric alcohols may be partially or fully hydrogenatedto accommodate end use requirements. The hydrogenation process that maybe used is described in U.S. patent publication 2012-0264664A1.

Lubricants and Functional Fluids

The lubricant and/or functional fluid compositions of the invention maycomprise one or more of the above-identified maleinized esterderivatives. These derivatives may be useful as viscosity modifiers,solubility improvers, performance boosters, and the like, as well asbase oils. These derivatives, when used as base oils, may be referred toas functional base oils. These derivatives may be blended with one ormore conventional base oils.

The lubricant compositions may be effective as engine oil or crankcaselubricating oils for spark-ignited and compression-ignited internalcombustion engines, including automobile and truck engines, two-strokecycle engines, aviation piston engines, marine and diesel engines,stationary gas engines, and the like. The lubricant compositions maycomprise engine oils. The functional fluids may comprise a drivelinefluid such as an automatic transmission fluid, manual transmissionfluid, transaxle lubricant, fluid for continuously variabletransmissions, dual clutch automatic transmission fluid, farm tractorfluid, fluids for hybrid vehicle transmission, or gear oil. Thefunctional fluid may comprise a metal-working lubricant, hydraulicfluid, or other lubricating oil or grease composition.

The maleinated ester derivatives may be biodegradable and may be used asfunctional base oils. The functional base oil may have a kineticviscosity (ASTM D-445) in the range from about 2 to about 1000 cSt at100° C., or from about 2 to about 500, or from about 2 to about 100, orfrom about 4 to about 10 cSt. The base oil may have a viscosity up toabout 35 cSt at 100° C., or in the range from about 3 to about 35 cSt,or in the range from about 5 to about 35 cSt at 100° C.

The functional base oil may have a viscosity index (ASTM D2270) in therange from about 120 to about 250, or from about 130 to about 170.

The functional base oil may have a pour point (ASTM D97) in the rangefrom about −20 to about −70° C., or from about −30 to about −45° C., orabout −40° C.

The functional base oil may have an aniline point (ASTM D611) in therange from about 25 to about 120° C., or from about 50 to about 100° C.

The functional base oil may have oxidation induction time (ASTM D6186)at 210° C. in the range from about 1 to about 10 minutes, or from about1 to about 3 minutes, or from about 5 to about 10 minutes.

The functional base oil may have an oxidation onset temperature (ASTME2009) in the range from about 170° C. to about 220° C., or from about190° C. to about 210° C.

The cold crank simulator viscosity test values (ASTM D5293) for thefunctional base oil may be in the range from about 13000 to about 9500cP, or from about 7000 to about 9500 cP, at a temperature of −15° C.; orin the range from about 7000 to about 6600 cP, or from about 1000 toabout 6200 cP, at a temperature of −35° C.

The evaporation loss (ASTM D5293) for the functional base oils may be inthe range from about 5 to about 15%, or from about 4 to about 7%.

The functional base oils may exhibit enhanced values for hightemperature shear stability, fuel economy, deposit control, oxidativestability, thermal stability, and the like.

The functional base oil may be used alone as the base oil or may beblended with an American Petroleum Institute (API) Group I, II, III, IVor V base oil, a natural oil, an estolide fluid, or a mixture of two ormore thereof. Examples of the natural oil may include soybean oil,rapeseed oil, and the like. The blended base oil may contain from about1% to about 75%, or from about 5% to about 60% by weight of themaleinized ester derivative.

The API Group I-V base oils have the following characteristics:

Base Oil Sulfur Saturates Viscosity Category (%) (%) Index Group I >0.03and/or <90 80 to 120 Group II ≦0.03 and ≧90 80 to 120 Group III ≦0.03and ≧90 ≧120 Group IV All polyalphaolefins (PAO) Group V All others notincluded in Groups I, II, III, or IV

The Group I-III Base Oils are Mineral Oils.

The base oil may be present in the lubricant or functional fluidcomposition at a concentration of greater than about 60% by weight basedon the overall weight of the lubricant or functional fluid composition,or greater than about 65% by weight, or greater than about 70% byweight, or greater than about 75% by weight.

When the maleinated ester derivatives are blended with polyalphaolefinsto make up the base oil, the maleinated ester derivatives may comprisefrom about 10% to about 80%, or from about 20% to about 60%, or about30% by weight of the base oil.

The polyalphaolefins blended with the maleinated ester derivates to makeup the functional base oil may comprise any API Group IVpolyalphaolefin. These may include poly(1-hexene), poly(1-octene),poly(1-decene), mixtures of two or more thereof, and the like. Thepolyalphaolefin may comprise a PAO-4, PAO-8, PAO-12, PAO-20, or amixture of two or more thereof. The term “PAO-4” refers to apolyalphaolefin with a kinematic viscosity at 100° C. of about 4(typically about 3 to 5) mm²/s as determined by Test Method GB/T265. Theterm “PAO-8” refers to a polyalphaolefin with a kinematic viscosity at100° C. of about 8 (typically about 7 to 9) mm²/s. The term “PAO-12”refers to a polyalphaolefin with a kinematic viscosity at 100° C. ofabout 12 (typically about 11 to 13) mm²/s. The term “PAO-20” refers to apolyalphaolefin with a kinematic viscosity at 100° C. of about 20 mm²/s.

The lubricant or functional fluid may further comprise one or moredispersants and/or detergents. The dispersant may be present in thelubricant or functional fluid composition at a concentration in therange from about 0.01 to about 20% by weight, or from about 0.1 to about15% by weight based on the weight of the lubricant or functional fluid.The detergent may be present in the lubricant or functional fluidcomposition at a concentration in the range from about 0.01% by weightto about 50% by weight, or from about 1% by weight to about 30% byweight based on the weight of the lubricant or functional fluidcomposition. The detergent may be present in an amount suitable toprovide a TBN (total base number) in the range from about 2 to about 100to the lubricant composition, or from about 3 to about 50. TBN is theamount of acid (perchloric or hydrochloric) needed to neutralize all orpart of a material's basicity, expressed as milligrams of KOH per gramof sample.

The detergent may include one or more overbased materials prepared byreacting an acidic material (typically an inorganic acid or lowercarboxylic acid, such as carbon dioxide) with a mixture comprising anacidic organic compound, a reaction medium comprising at least oneinert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) forsaid acidic organic material, a stoichiometric excess of a metal base,and a promoter such as a calcium chloride, acetic acid, phenol oralcohol. The acidic organic material may have a sufficient number ofcarbon atoms to provide a degree of solubility in oil. The metal may bezinc, sodium, calcium, barium, magnesium, or a mixture of two or morethereof. The metal ratio may be from an excess of 1 to about 40, or inthe range from about 1.1 to about 40. These detergents may includeoverbased sulfonates, overbased phenates, mixtures thereof, and thelike.

The dispersant that may be used may include any dispersant known in theart which may be suitable for the lubricant or functional fluidcompositions of this invention. These may include:

(1) Reaction products of carboxylic acids (or derivatives thereof), withnitrogen containing compounds such as amines, hydroxy amines, organichydroxy compounds such as phenols and alcohols, and/or basic inorganicmaterials. These may be referred to as carboxylic dispersants. These mayinclude succinimide dispersants, such as polyisobutenylsuccinimide.

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, for example, polyalkylene polyamines.These may be referred to as “amine dispersants.”

(3) Reaction products of alkylphenols with aldehydes (e.g.,formaldehyde) and amines (e.g., polyalkylene polyamines), which may bereferred to as “Mannich dispersants.”

(4) Products obtained by post-treating the carboxylic, amine or Mannichdispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like.

(5) Interpolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates oracrylamides and poly-(oxyethylene)-substituted acrylates. These may bereferred to as “polymeric dispersants.”

The lubricant or functional fluid composition may further comprise oneor more additional functional additives, including, for example, one ormore corrosion-inhibiting agents, oxidation-inhibiting agents, pourpoint depressing agents, extreme pressure (EP) agents, antiwear agents,viscosity index (VI) improvers, friction modifiers (e.g., fatty frictionmodifiers), hindered amine, phenolic and/or sulfurized inhibitors,antioxidants, metal cutting additives (e.g., sulfur chloride),antimicrobial additives, color stabilizers, viscosity modifiers (e.g.,ethylene propylene diene (EPDM) viscosity modifiers), demulsifiers, sealswelling agents, anti-foam agents, mixtures of two or more thereof, andthe like.

Extreme pressure (EP) agents and corrosion and oxidation-inhibitingagents which may be included in the lubricants and/or functional fluidsof the invention, may include chlorinated aliphatic hydrocarbons such aschlorinated wax; organic sulfides and polysulfides such as benzyldisulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurizedmethyl ester of oleic acid, sulfurized alkylphenol, sulfurizeddipentene, and sulfurized terpene; phosphosulfurized hydrocarbons suchas the reaction product of a phosphorus sulfide with turpentine ormethyl oleate, phosphorus esters including principally dihydrocarbyl andtrihydrocarbyl phosphites such as dibutyl phosphite, diheptyl phosphite,dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenylphosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthylphosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecularweight 500)-substituted phenyl phosphite, diisobutyl-substituted phenylphosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate,and barium heptylphenyl dithiocarbamate; Group II metalphosphorodithioates such as zinc dicyclohexylphosphorodithioate, zincdioctyl phosphorodithioate, barium di(heptylphenyl)phosphorodithioate,cadmium dinonyl phosphorodithioate, and the zinc salt of aphosphorodithioic acid produced by the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol and n-hexylalcohol.

Many of the above-mentioned extreme pressure agents andcorrosion-oxidation inhibitors may also serve as antiwear agents. Zincdialkyl phosphorodithioates are examples of such multifunctionaladditives.

Pour point depressants may be used to improve low temperature propertiesof the oil-based compositions. Examples of useful pour point depressantsmay include polymethacrylates; polyacrylates; polyacrylamides;condensation products of haloparaffin waxes and aromatic compounds;vinyl carboxylate polymers; and terpolymers of dialkyl fumarates, vinylesters of fatty acids, alkyl vinyl ethers, or mixtures of two or morethereof.

The viscosity modifiers may include one or more polyacrylates,polymethacrylates, polyolefins, and/or styrene-maleic ester copolymers.

Anti-foam agents may be used to reduce or prevent the formation ofstable foam. The anti-foam agents may include silicones, organicpolymers, and the like.

The lubricant or functional fluid may include one or more thickeners toprovide the lubricant or functional fluid with a grease-likeconsistency. The thickener may comprise lithium hydroxide, lithiumhydroxide monohydrate, or a mixture thereof. The thickener may comprise9-decenoic acid diol.

The functional additives may be added directly to the lubricant orfunctional fluid composition. Alternatively, the additives may bediluted with a substantially inert, normally liquid organic diluent suchas mineral oil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate, which may then be added to the lubricant and/or functionalfluid. The functional additives may include the maleinized esterderivatives of the invention. These concentrates may contain from about0.1 to about 99%, or from about 10% to about 90% by weight, of one ormore of the additives. The remainder of the concentrate may comprise thesubstantially inert normally liquid diluent.

The following examples are provided to illustrate the invention.

Example 1

0.355 kg (4.03 mol) 1-pentanol is charged to a reaction flask that isequipped with a thermocouple, addition funnel, nitrogen inlet, magneticstirrer, and short-path distillation bridge. The alcohol is heated to110° C. and methanesulfonic acid (1.5 mL, 70% aqueous solution) isadded. Maleinized methyl 9-dodecenoate (0.32 kg, AV=420 mg KOH/g) isadded dropwise using the addition funnel. The term “AV” refers to acidvalue. A reaction occurs. A terniary mixture of water, methanol andpentanol is removed via distillation. After the addition of the methyl9-dodecenoate is completed the resulting reaction mixture is heated to120° C. for an additional hour. The AV is monitored to observe thereaction progress, which is about 20. The temperature is furtherincreased to remove excess 1-pentanol and obtain an AV<2. The reactionmixture is allowed to cool to room temperature and vacuum (2 torr) isapplied to remove residual water and alcohol. The temperature isstepwise increased to 160° C. to remove all volatiles. The remainingester product is filtered over a bed of silica (1 inch (2.54 cm) frittedfunnel) by applying vacuum. The filtration yields a golden to amber oil.The amount of desired product is 0.38 kg (71% yield). KV (100° C.)=5.0cSt; KV (40° C.)=24.73 cSt; and viscosity index (VI)=128.

Example 2

Maleinized methyl 9-dodecenoate (50 g, 0.16 mol), 1-decanol (90.2 g,0.58 mol), p-toluenesulfonic acid (1.5 g, 0.008 mol) and 50 milliliters(ml) of toluene are added to a one-liter, three-necked round-bottomflask at 23° C. under an air atmosphere. The flask is fitted with athermocouple temperature regulator with heating mantle, Dean-Stark trapwith condenser, and a stopper with a nitrogen needle inlet. Nitrogen gasis passed through the needle inlet into the head space of the apparatus(flow rate=2.5 ft³/hr (70.8 liters/hr)) for 10 minutes. The temperatureis increased to 115° C. After 60 minutes, the temperature is increasedto 120° C. After an additional 90 minutes, the temperature is increasedto 130° C. Approximately 12.8 ml of distillate is collected in theDean-Start trap. An aliquot of the reaction mixture is taken at 4 hoursinto the reaction and measured for AV=2.3 mg KOH/g. The reaction mixtureis stirred for another 2.5 hours (total reaction time 6.5 hours). Theheating source is removed and the reaction mixture is allowed to cool toambient temperature. Ethyl acetate (200 ml) is used to wash the reactionmixture using a separatory funnel. The resulting organic layer is washedwith a NaOH solution (0.97 g NaOH in 480 ml H₂O) followed by washingwith a saturated NaCl solution three times. The resulting organicsolution is concentrated by a rotorary evaporator (5 Torr, 60° C.) toremove ethyl acetate and excess alcohol. A triester product is separatedfrom residual alcohol and water by vacuum distillation (2 Torr, 25° C.to 135° C.). The triester product is in the form of a clear dark amberoil. Analysis of the product indicates a mass of 112 g; a yield of 94%;KV (100° C.)=8.05 cSt; KV (40° C.)=44.4 cSt; and viscosity index(VI)=152.

Example 3

Maleinized methyl 9-dodecenoate (100 g, 0.32 mol), 3-methylbutanol (125g, 1.42 mol), p-toluenesulfonic acid (3 g, 0.015 mol) and 100milliliters (ml) of toluene are added to a one-liter, three-neckedround-bottom flask at 23° C. under an air atmosphere. The flask isfitted with a thermocouple temperature regulator with heating mantle,Dean-Stark trap with condenser, and a stopper with a nitrogen needleinlet. Nitrogen gas is passed through the needle inlet into the headspace of the apparatus (flow rate=2.5 ft³/hr (70.8 liters/hr)) for 10minutes. The temperature is increased to 115° C. After 60 minutes, thetemperature is increased to 120° C. After an additional 90 minutes, thetemperature is increased to 130° C. Approximately 12.8 ml of distillateis collected in the Dean-Start trap. An aliquot of the reaction mixtureis taken at 4 hours into the reaction and measured for AV with theresult being a AV of 7.6. The reaction mixture is stirred for another2.5 hours (total reaction time 6.5 hours). The heating source is removedand the reaction mixture is allowed to cool to ambient temperature.Ethyl acetate (200 ml) is used to wash the reaction mixture using aseparatory funnel. The resulting organic layer is washed with a NaOHsolution (0.97 g NaOH in 480 ml H₂O) followed by washing with asaturated NaCl solution three times. The resulting organic solution isconcentrated by a rotorary evaporator (5 Torr, 60° C.) to remove ethylacetate and excess alcohol. A triester product is separated fromresidual alcohol and water by vacuum distillation (2 Torr, 25° C. to135° C.). The triester product is in the form of a clear dark amber oil.Analysis of the product indicates a mass of 147.9 g; a yield of 88%; KV(100° C.)=5.8 cSt; KV (40° C.)=33.5 cSt; and viscosity index (VI)=115.

Example 4

0.741 kg (8.4 mol) 2-methylbutanol is charged to a reaction flask thatis equipped with a thermocouple, addition funnel, nitrogen inlet,magnetic stirrer, and short-path distillation bridge. The alcohol isheated to 110° C. and methanesulfonic acid (3.0 mL, 70% aqueoussolution) is added. Maleinized methyl 9-dodecenoate (0.8 kg, AV=420 mgKOH/g) is added dropwise using the addition funnel. A reaction occurs. Aterniary mixture of water, methanol, and reactant alcohol is removed viadistillation. After the addition is completed the resulting reactionmixture is heated to 120° C. for an additional hour. The AV is monitoredto observe the reaction progress, which is about 20. The temperature isfurther increased to remove excess 2-methylbutanol and obtain an AV<2.The reaction mixture is allowed to cool to room temperature and vacuum(2 torr) is applied to remove residual water and alcohol. Thetemperature is stepwise increased to 160° C. to remove all volatiles.The remaining ester product is filtered over a bed of silica (1 inch(2.54 cm), fritted funnel) by applying vacuum. The filtration yields agolden to amber oil. The amount of desired product is 0.877 kg (65%yield). KV (100° C.)=5.99 cSt; KV (40° C.)=37.58 cSt; and viscosityindex (VI)=102.

Example 5

Maleinized methyl 9-dodecenoate (100 g, 0.32 mol), Exxal10 ((C₁₀branched alcohol from ExxonMobil), 179.2 g, 1.13 mol), p-toluenesulfonicacid (3 g, 0.015 mol) and 100 milliliters (ml) of toluene are added to aone-liter, three-necked round-bottom flask at 23° C. under an airatmosphere. The flask is fitted with a thermocouple temperatureregulator with heating mantle, Dean-Stark trap with condenser, and astopper with a nitrogen needle inlet. Nitrogen gas is passed through theneedle inlet into the head space of the apparatus (flow rate=2.5 ft³/hr(70.8 liters/hr)) for 10 minutes. The temperature is increased to 115°C. After 60 minutes, the temperature is increased to 120° C. After anadditional 90 minutes, the temperature is increased to 130° C.Approximately 12.8 ml of distillate is collected in the Dean-Start trap.An aliquot of the reaction mixture is taken at 4 hours into the reactionand measured for AV with the result being a TAN of 7.6. The reactionmixture is stirred for another 2.5 hours (total reaction time 6.5hours). The heating source is removed and the reaction mixture isallowed to cool to ambient temperature. Ethyl acetate (200 ml) is usedto wash the reaction mixture using a separatory funnel. The resultingorganic layer is washed with a NaOH solution (0.97 g NaOH in 480 ml H₂O)followed by washing with a saturated NaCl solution three times. Theresulting organic solution is concentrated by a rotorary evaporator (5Torr, 60° C.) to remove ethyl acetate and excess alcohol. A triesterproduct is separated from residual alcohol and water by vacuumdistillation (2 Torr, 25° C. to 135° C.). The triester product is in theform of a clear dark amber oil. Analysis of the product indicates a massof 149 g; a yield of 63%; KV (100° C.)=10.4 cSt; KV (40° C.)=79.9 cSt;and viscosity index (VI)=113.

Samples of products from Examples 1 to 5 are tested for viscosity indexor VI (ASTM D2270) with the results indicated in Table 1.

TABLE 1 Example Alcohol Viscosity Index 1 1-Pentanol 128 2 1-Decanol 1523 3-Methylbutanol 115 4 2-Methylbutanol 102 5 Exxal 10 (C₁₀ branchedalcohol) 113

Example 6

Maleinized methyl 9-dodecenoate is made by the reaction of methyl9-dodecenoate and maleic anhydride via an “Ene” reaction. The maleinizedmethyl 9-dodecenoate is then reacted with 1-pentanol in the presence ofmethane sulfonic acid in an esterification/transesterification reactionto form a mixture of a mono-triester and a di-triester. The followingreactants and catalyst are used:

Name CAS # Methyl 9-dodecenoate 39202-17-0 Maleic anhydride 108-31-61-Pentanol 71-41-0 Methanesulfonic acid 75-75-2

Step 1:

The apparatus for conducting the maleinization reaction process includesa reactor, stripper and filter. A flow sheet for the process is shown inFIG. 1. A fresh feed containing methyl 9-dodecenoate and maleicanhydride is added to the reactor, heated to 75-90° C. and agitated tomelt the maleic anhydride and mix it into the methyl 9-dodeconate. Thereaction temperature is 220° C.-240° C. The pressure in the reactor isapproximately 30 psig (206.8 kilopascals). The reaction mixture isstripped in the stripper at a temperature of 200° C. and a pressure of<2 Torr. The desired product, which is in the form of a maleinized esterintermediate, is separated from the unreacted reactants (and someintermediate), and filtered. The unreacted reactants are recycled to thereactor. A material balance for Step 1 of the process is as follows (allnumerical values being in kilograms):

Fresh Feed Recycle Product Methyl 9-dodecenoate 519.7 168.2 8.4 Maleicanhydride 256.3 120 — Mono-maleinized — 28.9 730 methyl 9-dodecenoateDi-maleinized methyl — — 35.6 9-dodecenoate

Step 2:

The esterification reaction process is conducted using the processillustrated in FIG. 2. The apparatus for conducting the esterificationprocess includes a reactor and a stripper. The reactor is setup with anoverhead system able to collect 5-10 liters of overhead condensate. Theprocess includes three separate reactions, namely, an anhydride ringopening reaction, an esterification reaction with the maleic anhydridegroup, and a transesterification reaction where the 1-pentanol replacesthe methyl ester group. 1-Pentanol (31.0 Kg) and methanesulfonic acid(0.253 Kg) are loaded into the reactor and heated to 110° C. withagitation. The maleinized ester intermediate from Step 1 (27.3 Kg) isadded over a 30 minute period. After the maleinized ester intermediateis added, the reactor is closed up and the nitrogen sparge is set at 140ml/min. The internal pressure is controlled and regulated at 45 psig(310 kilopascals). The temperature of the reactor is increased to 160°C. After the reactor reaches 160° C., the pressure is slowly reduceduntil the overhead condensation rate is approximately 2 liters perminute. The pressure is continually decreased to meet the above overheadcondensate flow rate. Every hour from time zero, reactor samples aretaken to measure for AV. The pressure is continually decreased until itreaches 0 psig (0 kilopascals gauge pressure). At approximately, 3 hoursthe pressure is 0 psig (0 kilopascals) and TAN is equal to 5 mg KOH/g orbelow. An additional 6 L of pentanol and 0.253 Kg of methanesulfonicacid are added and the reaction pressure is increased to 20 psig (138kilopascals) or adjusted to maintain an overhead flow rate of 2 L perminute. The pressure is decreased slowly to maintain that flow rateuntil the pressure is 0 psig (0 kilopascals). At this point thetemperature is increased to 170° C. The reaction is terminated when theTAN is below 3 mg KOH/g. The reaction mixture is stripped at 175° C. and<2 Torr to separate unreacted pentanol (268.9 Kg) and methanesulfonicacid (about 1 Kg) from the esterified product. The esterified productcontains 41.5 Kg of a triester of the maleinized methyl 9-dodeconate.

The triester comprises a mixture of positional and olefin isomers. Themajor component (˜95%), a mono-triester, of this material is comprisedof a triester in isomeric form. Two proximal ester groups are separatedfrom a third ester group by an unsaturated carbon chain of C₁₁ to C₁₄ inlength. The proximal ester groups are separated by a C₄ saturated carbonchain. The minor component (˜5%), a di-triester, comprises five estergroups, where four proximal esters are separated from the fifth estergroups by an unsaturated carbon chain of C₁₁ to C₁₆ in length. The alkylportions of the ester groups have the structure nC₅H₁₂. These structuresare shown below.

Example 7

The triester from Example 6 is subjected to a hydrogenation reactionusing a transition metal, hydrogenation catalyst. The carbon-carbondouble bonds are converted to saturated carbon bonds with thehydrogenation reaction. The resulting structures are shown below.

Example 8

A triester derived from maleinized methyl 9-dodecenoate and 1-pentanolis blended with a polyalphaolefin base stock and an antioxidant to forma lubricating oil composition. This formulation is subjected to aSequence IIIG Engine Test with the results showing improved averageweighted piston deposit values. This indicates that fewer deposits areforming leading to a cleaner running engine. The lubricating oilformulation that is used is a SAE Viscosity 0W-20 oil which contains thefollowing ingredients:

Wt % Triester derived from maleinized methyl 9- 30.0 dodecenoate and1-pentanol PAO-4 polyalphaolefin 69.5 Irganox L57 (octylated/butylated0.5 diphenylamine antioxidant from Ciba Specialty Chemicals)

The Sequence IIIG Test is an industry standard fired-engine, dynamometerlubricant test for evaluating automotive engine oils for certainhigh-temperature performance characteristics, including oil thickening,varnish deposition, oil consumption, and engine wear. Such oils includeboth single viscosity grade and multi-viscosity grade oils that are usedin spark-ignition, gasoline-fueled engines, as well as diesel engines.

The Sequence IIIG Test utilizes a 1996 General Motors Powertrain 3800Series II, water-cooled, 4 cycle, V-6 engine as the test apparatus. TheSequence IIIG test engine is an overhead valve design (OHV) and uses asingle camshaft operating both intake and exhaust valves via pushrodsand hydraulic valve lifters in a sliding-follower arrangement. Theengine uses one intake and one exhaust valve per cylinder. Induction ishandled by a modified GM port fuel injection system setting theair-to-fuel ratio at 15:1. The test engine is overhauled prior to eachtest, during which critical engine dimensions are measured and rated ormeasured parts (pistons, camshaft, valve lifters, etc.) are replaced.

The Sequence IIIG Test consists of a 10-minute operational check,followed by 100 hours of engine operation at moderately high speed,load, and temperature conditions. The 100-hour segment is broken downinto five 20-hour test segments. Following the 10-minute operationalcheck and each 20-hour segment, oil samples are drawn from the engine.The kinematic viscosities of the 20-hour segment samples are compared tothe viscosity of the 10-minute sample to determine the viscosityincrease of the test oil. The results are indicated below.

Average Average Viscosity Cam + Weighted Piston Increase Lifter WearDeposits (%) (μm) (merits) Original Results 69.51 51.4 5.46 TransformedResults ^(B) 4.241471 3.9396 Industry Correction Factor 0.000000 0.00000.0000 Corrected Transformed 4.241471 3.9396 Severity Adjustment−0.497540 0.3594 0.4102 Final Transformed Result 3.743931 4.2990 FinalOriginal Unit Result 42.3 73.6 5.87 Oil Consumption Hours, h ^(C) 100Maximum Cam + Lifter Wear, μm 69 Average Oil Ring Plugging, % 0 AveragePiston Varnish, merits 9.70 Oil Consuption, L 2.71 Number of Cold-StuckRings 0 Number of Hot-Stuck Rings 0 ^(B) Viscosity Increase uses LN(PVIS), Average Cam + Lifter Wear uses LN (ACLW), Weighted PistonDeposits does not use a transformation ^(C) Test hours at which OilConsumption is calculated ^(D) Non-Reference Oil Tests Only

Viscosity Increase Data Results of ICP Analysis (cSt at 40° C.) of UsedOil^(C) Hours Viscosity Change Percent Hours Iron Copper Lead New 42.13Initial 8 2 2 Oil Initial^(B) 40.97 20 61 30 31 20 44.18 3.21 7.84 40118 35 36 40 46.77 5.80 14.16 60 172 34 38 60 49.94 8.97 21.89 80 250 3943 80 54.14 13.17 32.15 100  357 43 68 100  69.45 28.48 69.51 A 8000 cStis the Maximum Allowable Viscosity ^(B)at the End of Leveling Run^(C)Units are in ppm (parts per million).

Camshaft Lobe, Valve Lifter, Cam and Lifter Wear, Number μm μm μm 1 1 4950 2 3 38 41 3 3 46 49 4 11 48 59 5 3 47 50 6 8 45 53 7 3 44 47 8 5 4752 9 5 49 54 10 5 43 48 11 7 38 45 12 12 57 69 Maximum 12 57 69 Minimum1 38 41 Average 6 46 51.4

Oil Ring Land % Piston Deposit, Merits Chipped 1 8.65 0 2 5.82 0 3 3.320 4 1.90 0 5 6.73 0 6 8.07 0 Average 5.75 0.00

% Oil Ring Ring Sticking ^(A) Piston Plugging Hot-Stuck Rings Cold StuckRings 1 0 N N 2 0 N N 3 0 N N 4 0 N N 5 0 N N 6 0 N N Total 0 0 Average0 ^(A) Possible Values T = Top Compression Ring B = Bottom CompressionRing O = Oil Ring N = None

Grooves, merits Lands, merits Undercrown, 1 2 3 2 3 merits Piston 1 3.897.27 9.45 5.62 8.66 2.82 Piston 2 3.54 4.85 8.69 2.17 5.82 2.24 Piston 34.37 1.03 9.02 0.99 3.32 1.67 Piston 4 0.75 0.74 8.20 0.71 1.90 1.33Piston 5 0.75 3.73 8.93 0.85 6.73 1.94 Piston 6 1.97 3.10 9.31 1.62 8.072.19 WF 0.05 0.10 0.20 0.15 0.30 0.10 Note: These are UnweightedRatings.

Piston Skirt Varnish, merits Thrust Anti-Thrust Average Piston 1 9.9510.00 9.98 Piston 2 9.11 10.00 9.56 Piston 3 9.71 9.91 9.81 Piston 48.71 9.95 9.33 Piston 5 9.57 9.90 9.74 Piston 6 9.52 10.00 9.76 Average9.43 9.96 9.70 WF 0.10 PSVAVx = (PSTx + PSVAx)2 Where x = Number ofPiston PSVTAV = Average of Six Thrust Piston Skirt Ratings PSVAAV =Average of Six Anti-Thrust Piston Skirt Rating APV = Average of All 12Piston Ratings.

Total Weighted Deposits, merits Piston 1 7.53 Piston 2 5.65 Piston 34.42 Piston 4 3.49 Piston 5 5.51 Piston 6 6.13 Average Weighted Piston5.46 Deposits, merits WPDX = (WF*G1Px) + (WF*G2Px) + WF*G3Px) =(WF*L2P) + (WF*ORLDx) = (WF*UCPx) + (WF*PSVAVx) Where: x = Number ofPiston WF = Appropriate Weighting Factor (WF) for Part, From Table WPD =(WPD1 + WPD2 + WPD3 + WPD4 + WPD5 + WPD6)/6

Example 9

A maleinized ester derivative in the form of hydrogenated 1-pentyltriester of maleinated-9-dodecene methyl ester (hereinafter the “testsubstance”) is evaluated for aerobic biodegradability in watercontaining mineral salts and activated sludge. The activated sludge istaken from a wastewater treatment plant and is used as a source ofmicrobial inoculum. The objectives of the study are: 1) to evaluate thebiodegradability (mineralization to CO₂ production) potential of thetest substance in an aerobic, aqueous medium; and 2) to determine themineralization potential of a reference chemical in order to assess theviability of the test inoculum.

The test substance is in the form of a slight yellow oily liquid. It hasthe molecular formula C₃₂H₆₀O₆, and a carbon content of 71.07%.

The reference substance is sodium benzoate, CAS No. 532-32-1. Themolecular formula is C₆H₅COONa. The chemical purity of the referencesubstance is 99.9%.

The reagent water is purified, deionized and filtered.

Approximately one liter of activated sludge is used as the microbialinoculum. The sludge is collected from the Columbia Wastewater Plant inColumbia, Missouri. This plant treats predominately domestic sewage.

An aqueous mineral salts medium provides essential mineral nutrients andtrace elements necessary to sustain the inoculum throughout the testperiod. The mineral salts medium is prepared by addition of reagentgrade salts to reagent water. The mineral salts include salts of K, Na,NH₄, Ca, Mg and Fe. The pH of the mineral salts medium is 7.27.

Each test system consists of a 5-L Pyrex carboy (reaction flask orvessel) containing a 3.0 L test solution volume comprised of mineralsalts medium, prepared microbial inoculum, reagent water, and theappropriate test and/or reference substance additions. Outside air ispassed through a pre-trap containing 500 mL of approximately 5 N KOH.The air is then passed through approximately 500 mL of reagent water tohumidify the air, as well as to prevent contamination of the flasks fromthe KOH pre-trap. The CO₂-free and humidified air is then passed throughthe reaction flasks. This is shown in FIG. 5.

The CO₂-free air is introduced into each flask by positive pressure, andthe flow rates (50-100 mL/minute) are measured and adjusted using flowmeters. The outlet from each flask is connected to three CO₂ absorbergas-washing traps in series, each filled with 100 mL of 0.2 N KOHsolution. These traps capture the CO₂ evolved from the reaction flasks.A magnetic stir bar is placed in each flask. The flasks are placed oninsulated magnetic stir plates and stirred throughout the duration ofthe study. The test systems are kept in the dark (except for samplingand maintenance) in a temperature-controlled environmental chamber setat 22° C. Temperature of the chamber is continuously measured using aRees Scientific temperature monitoring system.

The activated sludge is homogenized in a blender at a medium speed fortwo minutes. The homogenized sludge is allowed to settle for 30 to 60minutes then filtered through glass wool. A volume of 30 mL of thefiltrate is used as the inoculum for each reaction flask.

The suspended solids concentration in each filtered solution isdetermined by filtering three 10 mL aliquots of sludge throughpre-weighed Whatman glass-fiber filter pads, followed by drying on aMettler HR73P halogen moisture analyzer. The increase in weight of thefilter pads is used to determine the suspended solids level. Thesuspended solids concentration of the prepared activated sludge isdetermined in the triplicate aliquots to be 0.4, 0.2, and 0.4 g/L, whichcorresponds to a mean of 0.3 g/L. The total concentration of suspendedsolids in each reaction flask (30 mL of inoculum to 3,000 mL of testmedium) is 3 mg/L.

A 1.00-mg/mL stock solution of the reference substance is prepared byweighing 500.8 mg of sodium benzoate into a 500-mL Class A volumetricflask, correcting for purity (99.9%), and bringing the solution tovolume with reagent water. The solution is stored refrigerated when notin use.

One day prior to dosing, six test systems are assembled. Each 5-L carboyreceives 2,400 mL of mineral salts medium and 30 mL of the preparedactivated sludge. Stirring and aeration with CO₂-free air atapproximately 90 mL/minute is started for each flask. The flasks areallowed to aerate overnight to purge the systems of CO₂ beforeinitiation of the test (dosing on Day 0).

Duplicate control systems are prepared by adding 570 mL of reagent waterto the 5-L carboys. The final volume is 3,000 mL.

Duplicate test substance systems are prepared by adding 570 mL ofreagent water and approximately 42.2 mg (dosed gravimetrically) of thetest substance to two of the 5-L carboys. The nominal concentration ofcarbon from the test substance in the final volume of 3,000 mL ofsolution is 10 mg C/L.

The reference substance system is prepared by adding 467 mL of reagentwater and 103 mL of the 1.00-mg/mL reference substance stock solution toa 5-L carboy. The nominal concentration of carbon from the referencesubstance in the final volume of 3,000 mL of solution is 20 mg C/L.

The toxicity control system is prepared by adding 467 mL of reagentwater, 103 mL of the 1.00-mg/mL reference substance stock solution, andapproximately 42.2 mg (dosed gravimetrically) of the test substance to a5-L carboy. The nominal concentration of carbon from the toxicity systemin the final volume of 3,000 mL of solution is 30 mg C/L.

After all additions, each of the reaction flasks are connected to aseries of three traps containing 100 mL of 0.2 N KOH. Aeration andstirring of the flasks are continued. Flow meters connected to the testsystems are adjusted to facilitate airflow at 50-100 mL/min. Thebubbling of air and stirring in each flask, as well as the bubbling ineach trap, confirms the constant aeration.

Approximately one hour after dosing, approximately 80 mL of each testsolution are removed, and the pH of each of the test solution ismeasured. One sample is filtered with a 0.45-μm nylon filter (sample fordissolved organic carbon (DOC) analysis) and both samples are depositedinto autosampler bottles, which are stored refrigerated until analysisfor dissolved organic carbon (DOC) and inorganic carbon (IC)concentrations.

The CO₂ produced in the test systems is trapped in the 0.2 N KOHsolutions, which are then analyzed for inorganic carbon (IC) content.Samples of the KOH solutions are collected for CO₂ analysis on Days 0,2, 6, 9, 12, 15, 19, and 29. For each sampling day, aliquots of the KOHsolution from the trap nearest each flask are placed into appropriatelylabeled glass autosampler vials. The vials are filled leaving noheadspace, capped using Teflon septa, the caps wrapped in parafilm, andstored at room temperature until analysis. For each sample day, theremaining KOH solution in this trap is discarded and replaced with 100mL of a fresh 0.2 N KOH solution. The refilled trap is then rotated tothe position farthest from the carboy, and the other two traps are movedforward (nearer to the carboy) one position.

The test is terminated after 28 days of incubation. The pH of each testsolution is measured on Day 28 of the test. After sampling the testsolutions, 1 mL of concentrated HCl is added to each test solution todrive carbonates and the remaining CO₂ from solution. The flasks arethen re-sealed and allowed to aerate overnight. On Day 29, samples aretaken from the test carboys for IC analysis, duplicate aliquots of eachtrap are for IC analysis, and the traps are not refilled with 0.2 N KOH.

Bacterial plate counts are performed on the prepared activated sludgeprior to initiation and each replicate reaction flask solution at Day28. A dilution series of each sample is prepared in sterile, pH 7.2,phosphate-buffered water at 10⁻², 10⁻³, 10⁻⁴, 10⁻⁵, and 10⁻⁶. Duplicate1-mL aliquots of each dilution are directly analyzed by plate countingmethods patterned after methods described in Standard Methods for theExamination of Water and Wastewater. (See, American Public HealthAssociation (APHA), American Water Works Association (AWWA), and WaterEnvironment Federation (WEF). 1998. Standard Methods for the Examinationof Water and Wastewater, 20^(th) Edition, Part 9215 B, Pour PlateMethod). The bacterial growth medium is Plate Count Agar (DifcoLaboratories). The plates of inocula are incubated at 26±2° C. for fiveto six days before counting the number of colonies on plates with fewerthan 300 colonies. The number of colonies at the dilution coming closestto 300 colonies is used to calculate colony forming units (CFU)/mL foreach sample.

DOC and IC analyses are conducted using a Teledyne Fusion Persulfate TOC(Total Organic Carbon) Analyzer. DOC is conducted using the TOC mode.Inorganic carbon analyses is conducted using the IC mode.

For IC and DOC analysis, three injections of each sample are made. Themean, SD, and CV are calculated for each sample. The mean value isreported as the carbon content of the sample in mg C/L.

Primary standards for total carbon (TC) analyses are made usingpotassium hydrogen phthalate prepared in HPLC-grade water. Primarystandards for inorganic carbon (IC) analyses are made using sodiumbicarbonate prepared in HPLC-grade water. Dilutions of the TC and ICprimary standards are used as working standards to calibrate each carbonanalyzer. A second set of the IC primary standard and dilutions isprepared and used as standards to check the performance of the carbonanalyzers during each analysis. All dilutions of primary standards areprepared using HPLC-grade water. The HPLC-grade water that is used ismanufactured by Fisher.

Calculations are performed using Microsoft Office Excel. Values are notrounded during the calculations. Final results are assigned by simplerounding (i.e., digits 0-4 round down and digits 5-9 round up).

The carbon analyzer calculates inorganic carbon concentrationsautomatically as mg C/L, based on comparison to carbon standardsolutions. The mg C/trap at each sampling point for each flask iscalculated as follows:

${\begin{pmatrix}{{Calculated}\mspace{14mu} {mg}\mspace{14mu} C\text{/}L} \\{{from}\mspace{14mu} {TOC}\mspace{14mu} {analyzer}}\end{pmatrix} \times \begin{pmatrix}{0.1\mspace{14mu} L\mspace{14mu} {volume}\mspace{14mu} {of}} \\{{gas}\text{-}{washing}\mspace{14mu} {bottles}}\end{pmatrix}} = \left( \frac{{mg}\mspace{14mu} C}{trap} \right)$

For the control systems, the evolved mg CO₂ is calculated as follows:

${\left\lbrack {\begin{pmatrix}{{mg}\mspace{14mu} C\text{/}L} \\{{from}\mspace{14mu} {trap}}\end{pmatrix} - \begin{pmatrix}{{mg}\mspace{14mu} C\text{/}L\mspace{14mu} {from}} \\{{freshly}\mspace{14mu} {prepared}\mspace{14mu} {KOH}}\end{pmatrix}} \right\rbrack \times \left( \frac{C\; O_{2}\mspace{14mu} {{wt}.}}{C\mspace{14mu} {{wt}.}} \right) \times \begin{pmatrix}{0.1\mspace{14mu} L} \\{{volume}\mspace{14mu} {of}\mspace{14mu} {gas}} \\{{washing}\mspace{14mu} {bottles}}\end{pmatrix}} - \begin{pmatrix}{evolved} \\{{mg}\mspace{14mu} {CO}_{2}}\end{pmatrix}$

The carbon to carbon dioxide factor used is 3.664 [from 44.01(CO₂)/12.01 (C)]. The cumulative evolved mg CO₂ is then calculated foreach control flask by summing values from successive days.

For flasks receiving test or reference substance, the net mg C producedis calculated for each sample point as follows:

${\frac{{mg}\mspace{14mu} C_{T}}{trap} - \frac{{mg}\mspace{14mu} C_{IB}}{trap}} = \frac{{Net}\mspace{14mu} {mg}\mspace{14mu} C}{trap}$

where:

mg C_(T)/trap=calculated mg C/trap value for the test or reference flask

mg C_(IB)/trap=average calculated mg C/trap value for the control flasks

Percent theoretical CO₂ (% ThCO₂) production from each test andreference system is calculated as follows:

${\frac{{Cumulative}\mspace{14mu} {Net}\mspace{14mu} {Trapped}\mspace{14mu} {Carbon}\mspace{14mu} \left( {{mg}\mspace{14mu} C} \right)}{{Applied}\mspace{14mu} {Theoretical}\mspace{14mu} {Carbon}\mspace{14mu} \left( {{mg}\mspace{14mu} C} \right)} \times 100} = {\% \mspace{14mu} {Th}\; C\; O_{2}}$

The volume of test and reference solutions after DOC sampling atinitiation is 2.92 L (from the 3,000 mL total volume, approximately 80mL (two autosampler bottles for DOC and IC analysis) are removed afterdosing.

The applied theoretical carbon in the reference substance systems iscalculated based on the volume of reference substance solution added tothe reaction flask, the concentration of the reference substancesolution, the percent carbon of the reference substance, and the totalvolume of testing medium in the reaction flask. The applied carbon forthe reference substance system is calculated as follows.

${{Applied}\mspace{14mu} {Th}\; C\; O_{2}\mspace{14mu} {Reference}\mspace{14mu} {Substance}} = {\frac{\left\lbrack {103\mspace{14mu} {mL} \times 1.00\mspace{14mu} {mg}\text{/}{mL} \times 58.34\% \mspace{14mu} C \times 2.92\mspace{14mu} L} \right\rbrack}{3.00\mspace{14mu} L} = {58.5\mspace{14mu} {mg}\mspace{14mu} C}}$

The applied theoretical carbon in the test substance systems iscalculated based on the mass of test substance added to the reactionflask, the percent carbon of the test substance, the percent purity ofthe test substance, and the total volume of testing medium in thereaction flask. The applied theoretical carbon for the test substancereplicate A flask is calculated as follows.

${{Applied}\mspace{14mu} {Th}\; C\; O_{2}\mspace{14mu} {Test}\mspace{14mu} {Substance}} = {\frac{\left\lbrack {42.5\mspace{14mu} {mg} \times 71.07\% \times 100\% \times 2.92\mspace{14mu} L} \right\rbrack}{3.00\mspace{14mu} L} = {29.4\mspace{14mu} {mg}\mspace{14mu} C}}$

The applied theoretical carbon in the toxicity control systems iscalculated based on the mass of test substance added to the reactionflask, the percent carbon of the test substance, the percent purity ofthe test substance, and the total volume of testing medium in thereaction flask in addition to the volume of reference substance solutionadded to the reaction flask, the concentration of the referencesubstance solution, the percent carbon of the reference substance, andthe total volume of testing medium in the reaction flask. The appliedtheoretical carbon for the toxicity control is equal to that of thereference substance system and the test substance system combined, for atotal of 87.7 mg C.

The percent DOC removed from each test and reference substance system iscalculated and determined as follows:

${\left\lbrack {1 - \left( \frac{T_{28} - {B\; L_{28}}}{T_{0} - {B\; L_{0}}} \right)} \right\rbrack \times 100} = {\% \mspace{14mu} {DOC}\mspace{14mu} {Removed}}$

where:

T₀, T₂₈=DOC (mg C/L) measured from the test or reference flask reactionsolutions at Days 0 and 28

BL₀, BL₂₈=Average DOC (mg C/L) measured from the control flask reactionsolutions at Days 0 and 28

The pH of the control solutions are 7.66 and 7.62 at study initiationand 7.50 and 7.56 at termination for replicates A and B, respectively.The pH of the test substance solutions are 7.72 and 7.60 at studyinitiation and 7.65 and 7.58 at termination for replicates A and B,respectively. The pH of the reference substance system increases from7.61 at study initiation to 7.84 at study termination. The pH of thetoxicity control system is 7.64 at study initiation and 7.77 at studytermination. All pH values are suitable for biological systems

The average temperature of the environmental chamber ranges from 21.06to 21.91° C. during the test duration.

At study initiation, DOC in the control solutions is not detected. Atstudy termination, the mean DOC concentration of the control solutionsis not detected.

At study initiation, DOC concentration in the test substance replicatesis not detected. The mean corrected DOC concentrations of the testsubstance solutions at termination is 3.35 mg C/L. The test substance isinsoluble in water, so the result showing minimal to no DOC atinitiation is expected. The increase in DOC concentration from Day 0 toDay 28 is likely due to the insolubility of the test substance in water(that is, more test substance likely went into solution while stirringover time). Consequently, DOC removal cannot be calculated for the testsubstance.

At study initiation, the corrected DOC concentration of the referencesubstance solution is 21.0 mg C/L, which confirms the dose rate of 20 mgC/L. The corrected DOC concentration of the reference substance solutionat termination is 0.00 mg C/L, corresponding to 100% DOC removal.

At study initiation, the corrected DOC concentration of the toxicitycontrol is 21.4 mg C/L, which is consistent with the above (i.e. 20 mgC/L of reference substance and test substance being insoluble socontributing no DOC). The corrected DOC concentration of the toxicitycontrol at termination is 3.65 mg C/L.

At study initiation, the IC concentrations of the control solutions are0.0133 and 0.0501 mg C/L for replicates A and B, respectively. Themeasured IC concentration of the test substance solutions at initiationis 0.5690 and 0.0000 mg C/L for replicates A and B, respectively. Afteradjustment for control IC concentrations, the average IC concentrationfor the test substance solutions is 0.25 mg C/L. This value correspondsto 2.53% of the total carbon (TC). The IC concentration of the referencesubstance solution at initiation, after adjustment for the mean of thecontrol, is 0.79 mg C/L or 3.79% of the TC concentration. The ICconcentration of the toxicity control solution at initiation, afteradjustment for the mean of the control, is 0.54 mg C/L or 1.76% of theTC concentration. These results show that inorganic carbon does notsignificantly contribute to background levels of carbon in the testsystems.

The bacterial plate counts prior to initiation show that the preparedactivated sludge contains 9.2×10⁴ CFU/mL. The results of bacterial platecounts at study termination show that the controls contain 2.2×10⁴CFU/mL for replicate A and 2.0×10⁴ CFU/mL for replicate B. The testtreatment replicates A and B contain 2.4×10⁴ and 3.7×10⁴ CFU/mL,respectively. The reference substance treatment contains 1.4×10⁴ CFU/mL.The toxicity control contains 1.7×10⁴ CFU/mL. This microbial evaluationdata suggests the test substance has no significant effect on thepopulation of microbes, and the microbial populations in the inoculumare viable.

CO₂ evolved from the control system is 236.8 and 146.7 mg CO₂, by Day 29of the study for replicate A and B, respectively. These values arecorrected for the background CO₂ present in the fresh KOH solutions. Thegoal of the control systems are to provide the background CO₂ valuesresulting from the endogenous CO₂ evolution from the microbial inoculum.The total mg CO₂ evolved from the control system is divided by 3 (litersof solution per flask) to give mg CO₂/L. The total mg CO₂ evolved fromthe control system, 191.7 mg CO₂ (63.9 mg CO₂/L) is higher than 40 mgCO₂/L, however is still within the upper limit indicated in the protocol(<70 mg CO₂/L or 210 mg CO₂/flask).

The test substance exhibits mean % ThCO₂ values of 15.8% and 71.6%(after correction for background CO₂ from the controls) at Day 9 and Day19 of the study, respectively. The test substance exhibits % ThCO₂values of 63.8% for replicate A and 79.4% for replicate B at Day 19 ofthe study, and the replicates are within 20% of each other at the end ofthe 10-day window. Since biodegradation values exceeds 60% ThCO₂ withina 10 day window, these results indicate that the test substance may beclassified as readily biodegradable

The reference substance exhibits a % ThCO₂ value of 67.2% on Day 9 ofthe study. The value through Day 29 of the study is 73.7% ThCO₂. Theresults from Day 9 (67.2% ThCO₂ evolved) indicate greater than 60% ThCO₂evolved in the first 9 days of the test. These results indicate that theinoculum is viable according to the criteria outlined in the applicabletesting guideline.

The toxicity control, sodium benzoate plus the test substance, exhibit a% ThCO₂ value of 47.5% on Day 6 of the study. The value through Day 29of the study is 72.8% ThCO₂. Since the biodegradation value is greaterthan 25% ThCO₂ by day 6, the test substance can be assumed to not beinhibitory.

The mean percent theoretical CO₂ produced by the test substance is 15.8%by Day 9 of the study and 71.6% by Day 19 of the study. Since thebiodegradation value exceeds 60% ThCO₂ within a 10-day window, the testsubstance can be classified as readily biodegradable.

The percent theoretical CO₂ produced by the reference substance is 67.2%by Day 9 of the study, confirming the inoculum is viable. The percenttheoretical CO₂ produced by the toxicity control is 47.5% by Day 6 ofthe study, confirming the triester is not inhibitory.

While the invention has been explained in relation to variousembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein includes any such modifications that may fall withinthe scope of the appended claims.

1. A composition comprising a maleinized ester derivative made by thereaction of: (i) an unsaturated linear aliphatic carboxylic acid methylester comprising a linear hydrocarbon chain of about 8 to about 18carbon atoms; and (ii) maleic anhydride; and (iii) a monohydric alcoholof 3 to about 12 carbon atoms; wherein the maleinized ester derivativecomprises at least two proximal ester groups and another ester group,the proximal ester groups and the another ester group containingstraight chain alkyl groups of 3 to about 12 carbon atoms; the proximalester groups being separated from the another ester group by at leastabout 8 carbon atoms.
 2. The composition of claim 1 wherein theunsaturated linear aliphatic carboxylic acid methyl ester is reactedwith the maleic anhydride to form a maleinized unsaturated carboxylicacid methyl ester, and the maleinized unsaturated carboxylic acid methylester is reacted with the monohydric alcohol to form the maleinizedester derivative.
 3. The composition of claim 2 wherein prior to thereaction with the monohydric alcohol, the maleinized carboxylic acidmethyl ester comprises a methyl ester group and a maleic anhydridegroup, the reaction with the monohydric alcohol comprising anesterification reaction with the maleic anhydride group and atransesterification reaction with the methyl ester group.
 4. Thecomposition of claim 2 wherein prior to the reaction with the monohydricalcohol, the maleinized carboxylic acid methyl ester comprises a methylester group and two maleic anhydride groups, the reaction with themonohydric alcohol comprising an esterification reaction with the maleicanhydride groups and a transesterification reaction with the methylester group.
 5. The composition of claim 1 wherein the monohydricalcohol comprises a linear alcohol.
 6. The composition of claim 1wherein the maleinized ester derivative comprises a mono-triester, or amixture of a mono-triester and a di-triester.
 7. The composition ofclaim 1 wherein the maleinized ester derivative contains one or morecarbon-carbon double bonds, the one or more carbon-carbon double bondsbeing hydrogenated to form saturated carbon bonds.
 8. The composition ofclaim 1 claims wherein the unsaturated linear aliphatic carboxylic acidmethyl ester comprises methyl 8-nonenoate, methyl 9-decenoate, methyl10-undecenoate, methyl 9-dodecenoate, methyl 9-octadecenoate, or amixture of two or more thereof.
 9. The composition of claim 1 whereinthe monohydric alcohol comprises 1-propanol, 1-butanol, 1-pentanol,1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-undecanol, 1-dodecanol,2-methyl butanol, 3-methyl butanol, a C₁₀ branched alcohol, or a mixtureof two or more thereof.
 10. The composition of claim 1 wherein theunsaturated linear aliphatic carboxylic acid methyl ester comprisesmethyl 9-dodecenoate and the monohydric alcohol comprises 1-pentanol.11. The composition of claim 1 wherein the unsaturated linear aliphaticcarboxylic acid methyl ester is derived from a natural product.
 12. Thecomposition of claim 1 wherein the unsaturated linear aliphaticcarboxylic acid methyl ester is derived from vegetable oil, algae oil,fungus oil, animal oil, animal fat, sucrose, lactose, glucose, fructose,canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, oliveoil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil,sunflower seed oil, tall oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard oil, camellina oil, pennycress oil, castor oil,coriander oil, almond oil, wheat germ oil, bone oil, lard, tallow,poultry fat, algae oil, yellow grease, fish oil, sugar cane, sugar beet,corn syrup, or a mixture of two or more thereof.
 13. The composition ofclaim 1 wherein the unsaturated linear aliphatic carboxylic acid methylester is derived from a natural product, the natural oil comprising arefined, bleached and/or deodorized natural product.
 14. The compositionof claim 13 wherein the refined, bleached and/or deodorized naturalproduct comprises soybean oil.
 15. The composition of claim 1 whereinthe unsaturated linear aliphatic carboxylic acid methyl ester is derivedfrom a metathesized natural product or a metathesized natural productderived unsaturated carboxylic acid and/or ester.
 16. The composition ofclaim 15 wherein the metathesized natural product or metathesizednatural product derived unsaturated carboxylic acid and/or ester is madeby reacting one or more natural products and/or natural product derivedunsaturated carboxylic acids and/or esters in the presence of ametathesis catalyst.
 17. The composition of claim 15 wherein themetathesized natural product or metathesized natural product derivedunsaturated carboxylic acid and/or ester is made by reacting one or morenatural products and/or natural product derived unsaturated carboxylicacids and/or esters with another olefinic compound in the presence of ametathesis catalyst.
 18. The composition of claim 16 wherein themetathesis catalyst comprises a metal carbene catalyst, the metal beingruthenium, molybdenum, osmium, chromium, rhenium, and/or tungsten. 19.The composition of claim 16 wherein the natural product or naturalproduct derived unsaturated carboxylic acid and/or ester is partiallyhydrogenated prior to the reaction in the presence of the metathesiscatalyst.
 20. A concentrate composition comprising from about 0.1% toabout 99% by weight of the composition of claim 1, and a normally liquiddiluent.
 21. A lubricant or functional fluid composition comprising thecomposition of claim
 1. 22. The lubricant or functional fluidcomposition of claim 21 wherein the composition further comprises an APIGroup I oil, Group II oil, Group III oil, Group IV oil, Group V oil,natural oil, estolide, or a mixture of two or more thereof.
 23. Thelubricant or functional fluid composition of claim 21 wherein thelubricant or functional fluid composition further comprises a detergent,dispersant, corrosion inhibitor, oxidation inhibitor, antiwear agent,friction modifier, pourpoint depressant, anti-foam agent, metaldeactivator, viscosity modifier, extreme pressure agent, demulsifier,seal swelling agent, or a mixture of two or more thereof.
 24. Thelubricant or functional fluid composition of claim 21 wherein thelubricant or functional fluid composition comprises a greasecomposition, the grease composition comprising lithium hydroxide,lithium hydroxide monohydrate, or a mixture thereof.
 25. A base oil foran engine oil comprising the composition of any of claim 1 and apolyalphaolefin.
 26. The base oil of claim 25 wherein thepolyalphaolefin is PAO-4.
 27. The base oil of claim 25 wherein the baseoil comprises a maleinated ester derivative, the base oil comprisingfrom about 10% to about 80% by weight of the maleinated esterderivative.
 28. The base oil of claim 25 further comprising anantioxidant.
 29. An engine oil comprising a polyalphaolefin and atriester derived from maleinized methyl 9-dodecenoate and 1-pentanol.30. The engine oil of claim 29 wherein the triester comprises a mixtureof a mono-triester and a di-triester.